EP1149390B1 - Process for producing self-extinguishing cables with low-level production of fumes and flame-retardant compositions used therein - Google Patents

Process for producing self-extinguishing cables with low-level production of fumes and flame-retardant compositions used therein Download PDF

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Publication number
EP1149390B1
EP1149390B1 EP99965500A EP99965500A EP1149390B1 EP 1149390 B1 EP1149390 B1 EP 1149390B1 EP 99965500 A EP99965500 A EP 99965500A EP 99965500 A EP99965500 A EP 99965500A EP 1149390 B1 EP1149390 B1 EP 1149390B1
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Prior art keywords
flame
retardant
composition
dehydrating agent
process according
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EP99965500A
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German (de)
English (en)
French (fr)
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EP1149390A1 (en
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Franco Peruzzotti
Diego Tirelli
Paolo Liboi
Enrico Albizzati
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Prysmian SpA
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Prysmian SpA
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B7/00—Insulated conductors or cables characterised by their form
    • H01B7/17—Protection against damage caused by external factors, e.g. sheaths or armouring
    • H01B7/29—Protection against damage caused by extremes of temperature or by flame
    • H01B7/295—Protection against damage caused by extremes of temperature or by flame using material resistant to flame
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K21/00—Fireproofing materials
    • C09K21/02—Inorganic materials

Definitions

  • the present invention relates to a process for producing cables, in particular electrical cables for low-voltage power transmission or for telecommunications, these cables having self-extinguishing properties and producing a low level of fumes, and to the flame-retardant compositions used therein.
  • Self-extinguishing cables are generally produced by extruding over the core of the cable a flame-retardant coating consisting of a polymer composition which has been given flame-resistant properties by the addition of a suitable additive.
  • a flame-retardant coating consisting of a polymer composition which has been given flame-resistant properties by the addition of a suitable additive.
  • Polyolefin-based compositions based, for example, on polyethylene or ethylene/vinyl acetate copolymers, containing an organic halide combined with antimony trioxide as flame-retardant additive can, for example, be used for this purpose.
  • halogenated flame-retardant additives have many drawbacks since they partially decompose during processing of the polymer, giving rise to halogenated gases that are toxic to workers and corrode the metal parts of the polymer-processing equipment. In addition, when they are placed directly in -a flame, their combustion gives rise to very large amounts of fumes containing toxic gases. Similar
  • halogen-free compounds in the production of self-extinguishing cables, in which a polymer base, generally of polyolefin type, is mixed with inorganic flame-retardant fillers, generally hydroxides, hydrated oxides or hydrated salts of metals, in particular of aluminium or magnesium, such as magnesium hydroxide or alumina trihydrate, or mixtures thereof (see, for example, patents US 4,145,404 , US 4,673,620 , EP 328,051 and EP 530,940 ).
  • the inorganic fillers can be used as they are or coated with various hydrophobic products, for example with saturated or unsaturated fatty acids or salts thereof, in particular oleic acid or stearic acid or the corresponding oleates or stearates, or with organic silanes or titanates.
  • patent application WO 96/27885 describes a flame-retardant composition for coating electrical cables, comprising polypropylene as polymer matrix supplemented with 1-20 % by weight of a polyethylene wax and 100-200 % by weight of magnesium hydroxide coated with a hydrophobic product, for example an alkylsilane (% by weight relative to the weight of the polypropylene).
  • This coating is said to increase the compatibility between the filler and the polymer matrix and at the same time to impart hydrophobic properties to the flame-retardant coating, thus avoiding the absorption of moisture which would reduce the efficiency of the insulating properties of the material.
  • Japanese patent application JP-07-161,230 describes polymer compositions with flame-retardant properties, containing appropriately ground natural magnesium hydroxide which has been surface-treated with a fatty acid or a salt thereof, or with a silane or a titanate, in amounts of between 0.5 and 5 % by weight relative to the weight of the hydroxide.
  • surface treatment of the filler is said to make it possible to reduce the absorption of moisture, thus preventing the water vapour released from the filler during the extrusion of the composition on the cable from effecting a kind of expansion of the material and a worsening of the surface appearance of the cable thus obtained.
  • the Applicant has observed that, in the production of self-extinguishing cables in which an inorganic filler as described above is used, coating of this filler with hydrophobic agents, as indicated in the prior art, is not sufficient to obtain a satisfactory result which is reproducible on an industrial scale, in particular when the process for extruding the flame-retardant composition is carried out at elevated temperatures in order to increase the fluidity and thus the processibility of the composition so as to obtain high extrusion rates and thus high productivity.
  • the Applicant has often observed, with flame-retardant fillers which are either coated or non-coated, and in particular with those of natural origin (i.e.
  • the Applicant has now found that it is possible to obtain a self-extinguishing cable with a flame-retardant coating which is substantially free of pores and which has a smooth and uniform outer surface, if a dehydrating agent is added to the composition comprising a polymer base and an inorganic flame-retardant filler.
  • This dehydrating agent can be added to the flame-retardant composition during the mixing (compounding) phase or directly upstream of the extruder.
  • the present invention thus relates to a process for producing self-extinguishing cables with low-level production of fumes, which comprises:
  • the dehydrating agent is added during phase (a) of preparation of the flame-retardant composition.
  • the dehydrating agent is added during phase (a) of preparation of the flame-retardant composition after a first phase of mixing the composition at a predetermined temperature and for a predetermined time so as to reduce the moisture content present in the flame-retardant filler.
  • the dehydrating agent is added during phase (b) of extrusion of the flame-retardant composition.
  • the present invention relates to a flame-retardant composition
  • a flame-retardant composition comprising a polymer base and an inorganic flame-retardant filler, characterized in that it also comprises a dehydrating agent.
  • the dehydrating agent exerts its action by absorbing the water present in the flame-retardant filler, which is released during the heating of the composition in the extrusion phase.
  • the mechanism of absorption is preferably of irreversible type, or the dehydrating agent can absorb the water reversibly but with a low rate of release of the moisture at the extrusion temperature, so as to ensure the virtual absence of water in the vapour state during the extrusion phase.
  • Working in this way prevents the formation of pores inside the flame-retardant coating and/or the appearance of roughness on its surface.
  • the amount of water released increases as the extrusion temperature increases, as a result of which the advantages deriving from the presence of the dehydrating agents become particularly evident when relatively high extrusion temperatures, generally above 180°C, preferably above 200°C, are used.
  • the Applicant has found that the effect of the dehydrating agent on the surface appearance and on the mechanical properties of the flame-retardant coating is particularly evident when flame-retardant fillers of natural origin are used, for example magnesium hydroxide obtained by grinding minerals such as brucite.
  • flame-retardant fillers of natural origin for example magnesium hydroxide obtained by grinding minerals such as brucite.
  • the reason for this is thought to be that a flame-retardant filler of natural origin contains large amounts of moisture, greater than the amounts typically found in synthetic flame-retardant fillers.
  • the moisture present can derive either from the starting mineral or from the grinding process to which this mineral is subjected, or can be absorbed from the surroundings.
  • Dehydrating agents which can be used are readily available inorganic compounds which are easy to handle, which do not adversely effect the mechanism of action of the flame-retardant filler and which do not produce toxic products if they are heated to high temperature or exposed to the direct action of a flame.
  • the dehydrating agent can be chosen from: calcium oxide, calcium chloride, anhydrous alumina, zeolites, magnesium sulphate, magnesium oxide, barium oxide, or mixtures thereof. Calcium oxide and zeolites, or mixtures thereof, are particularly preferred.
  • the amount of dehydrating agent to be added to the flame-retardant composition is mainly predetermined as a function of the nature and efficacy of this agent and on the amount of water present in the flame-retardant filler. In general, it is believed that an amount of dehydrating agent of between 0.5 and 15 % by weight, preferably between 1 and 10 % by weight, relative to the weight of the flame-retardant filler, is sufficient to ensure a satisfactory result.
  • Flame-retardant fillers which can generally be used are hydroxides, hydrated oxides, salts or hydrated salts of metals, in particular of calcium, aluminium or magnesium, such as: magnesium hydroxide, alumina trihydrate, hydrated magnesium carbonate, magnesium carbonate, hydrated calcium and magnesium carbonate, calcium and magnesium carbonate, or mixtures thereof.
  • magnesium hydroxide is particularly preferred, since it is characterized by a decomposition temperature of about 340°C and thus allows high extrusion temperatures to be used.
  • magnesium hydroxide of natural origin obtained by grinding minerals based on magnesium hydroxide, such as brucite, as described in European patent application WO 99/05688 , filed on 01.12.97 by the Applicant and in the publication on Research Disclosure No. 407 (March 1998).
  • the flame-retardant filler is generally used in the form of particles which are untreated or surface-treated with saturated or unsaturated fatty acids containing from 8 to 24 carbon atoms, or metal salts thereof, such as, for example: oleic acid, palmitic acid, stearic acid, isostearic acid, lauric acid; magnesium or zinc stearate or oleate.
  • the flame-retardant filler can likewise be surface-treated with suitable coupling agents, for example organic silanes or titanates such as vinyltriethoxysilane, vinyltriacetylsilane, tetraiso-propyl titanate, tetra-n-butyl titanate.
  • the amount of flame-retardant filler to be added is predetermined so as to obtain a cable which is capable of passing the ordinary fire-resistance tests, for example the test according to standards IEC 332-1 and IEC 332.3 A,B,C. In general, this amount is between 10 and 90 % by weight, preferably between 30 and 80 % by weight, relative to the total weight of the flame-retardant composition.
  • the polymer base can generally be chosen from:
  • Copolymers which are particularly preferred are those which can be obtained by copolymerization of ethylene with at least one ⁇ -olefin containing from 3 to 12 carbon atoms, and optionally with a diene, in the presence of a "single-site" catalyst, in particular a metallocene catalyst or a constrained geometry catalyst.
  • a single-site catalyst in particular a metallocene catalyst or a constrained geometry catalyst.
  • copolymers are characterized by a density of between 0.860 and 0.904 g/cm 3 , preferably from 0.865 to 0.902 g/cm 3 , and by a composition distribution index greater than 45 %, said index being defined as the percentage by weight of the copolymer molecules having an ⁇ -olefin content of up to 50 % of the total average molar content of ⁇ -olefin.
  • These copolymers preferably have the following monomer composition: 75-97 mol%, preferably 90-95 mol%, of ethylene; 3-25 mol%, preferably 5-10 mol%, of ⁇ -olefin; 0-5 mol%, preferably 0-2 mol%, of a diene.
  • the ⁇ -olefin is preferably chosen from propylene, 1-butene, 1-hexene, 1-octene. Products of this type are commercially available under the tradenames Engage® from Du Pont-Dow Elastomers and Exact® from Exxon Chemical.
  • the ethylene copolymers obtained by single-site catalysis are preferably used as a mixture with a crystalline propylene homopolymer or copolymer, as described, for example, in the abovementioned European patent application No. 97121042.2 , or with an ethylene homopolymer or copolymer which has a density of between 0.905 and 0.970 g/cm 3 , preferably between 0.910 and 0.940 g/cm 3 , as described, for example, in European patent application No. 98118194.4 filed on 25.9.98 in the name of the Applicant, or alternatively in US patent 5,707,732 .
  • the polymer base preferably comprises from 5 to 60 % by weight, more preferably from 10 to 45 % by weight, of a propylene or ethylene homopolymer or copolymer as defined above, and from 40 to 95 % by weight, more preferably from 55 to 90 % by weight, of an ethylene copolymer obtained by single-site catalysis, the percentages being relative to the total weight of the polymeric components (a) and (b).
  • a coupling agent capable of increasing the interaction between the active groups of the flame-retardant filler and the polymer chains may be added to the mixture in order to enhance the compatibility between the flame-retardant filler and the polymer matrix.
  • This coupling agent can be chosen from those known in the art, for example: saturated silane compounds or silane compounds containing at least one ethylenic unsaturation; epoxides containing an ethylenic unsaturation; monocarboxylic acids or, preferably, dicarboxylic acids having at least one ethylenic unsaturation, or derivatives thereof, in particular anhydrides or esters.
  • silane compounds which are suitable for this purpose are: ⁇ -methacryloxypropyltrimethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, allylmethyldimethoxysilane, allylmethyl-diethoxysilane, methyltriethoxysilane, methyltris-(2-methoxyethoxy)silane, dimethyldiethoxysilane, vinyltris(2-methoxyethoxy)silane, vinyltrimethoxysilane, vinylmethyldimethoxysilane, vinyltriethoxysilane, octyltriethoxysilane, isobutyltri-ethoxysilane, isobutyltrimethoxysilane, or mixtures thereof.
  • epoxides containing an ethylenic unsaturation are: glycidyl acrylate, glycidyl methacrylate, monoglycidyl ester of itaconic acid, glycidyl ester of maleic acid, vinyl glycidyl ether, allyl glycidyl ether, or mixtures thereof.
  • Monocarboxylic or dicarboxylic acids, having at least one ethylenic unsaturation, or derivatives thereof, which can be used as coupling agents are, for example: maleic acid, maleic anhydride, fumaric acid, citraconic acid, itaconic acid, acrylic acid, methacrylic acid, and anhydrides or esters derived from these, or mixtures thereof.
  • Maleic anhydride is particularly preferred.
  • the coupling agents can be used as they are or pregrafted onto a polyolefin, for example polyethylene or copolymers of ethylene with an ⁇ -olefin, by means of a radical reaction (see for example patent EP-530,940 ).
  • the amount of coupling agent grafted is generally between 0.05 and 5 parts by weight, preferably between 0.1 and 2 parts by weight, relative to 100 parts by weight of polyolefin.
  • Polyolefins grafted with maleic anhydride are available as commercial products known, for example, under the brand names Fusabond ® (Du Pont), Orevac ® (Elf Atochem), Exxelor ® (Exxon Chemical), Yparex ® (DSM), etc.
  • the coupling agents of carboxylic or epoxide type mentioned above for example maleic anhydride
  • the silanes with ethylenic unsaturation for example vinyltrimethoxysilane
  • a radical initiator so as to graft the compatibilizing agent directly onto the polymer matrix.
  • An organic peroxide such as tert-butyl perbenzoate, dicumyl peroxide, benzoyl peroxide, di-tert-butyl peroxide can, for example, be used as initiator.
  • This method is described, for example, in patent US-4,317,765 , in Japanese patent application JP-62-58774 or alternatively in the abovementioned European patent applications Nos. 97121042.2 and 98118194.4 .
  • the amount of coupling agent to be added to the mixture can vary mainly depending on the type of coupling agent used and on the amount of flame-retardant filler added, and is generally between 0.01 and 5%, preferably between 0.05 and 2%, by weight relative to the total weight of the base polymer mixture.
  • compositions according to the present invention can be added to the compositions according to the present invention.
  • antioxidants which are suitable for this purpose are, for example:
  • fillers which may be used in the present invention include, for example, glass particles, glass fibres, calcined kaolin, talc, or mixtures thereof.
  • Processing co-adjuvants usually added to the polymer base are, for example, calcium stearate, zinc stearate, stearic acid, paraffin wax, silicone rubbers, or mixtures thereof.
  • the flame-retardant compositions according to the present invention are preferably used in non-crosslinked form, in order to obtain a coating with thermoplastic properties which is thus recyclable.
  • the flame-retardant compositions according to the present invention can be prepared by mixing the polymer base, the flame-retardant filler, the dehydrating agent and the other additives which may be present according to techniques known in the art, for example using an internal mixer of the type containing tangential rotors (Banbury) or interlocking rotors, or in continuous mixers of the Ko-Kneader (Buss)type or of the co-rotating or counter-rotating twin-screw type.
  • the dehydrating agent is introduced after a first phase of processing the composition during which, on account of the heating generated by the compounding process, the flame-retardant filler loses a certain amount of the moisture absorbed. In this way, premature depletion of the water-absorbing capacity of the dehydrating filler is avoided, this filler needing to be active mainly during the subsequent extrusion phase.
  • the temperature of the composition in this first compounding phase is at least 100°C, preferably at least 150°C, and is carried out for a period of at least 5 minutes.
  • the dehydrating agent can be added during the extrusion phase, for example via the extruder hopper.
  • the dehydrating agent can be added to the flame-retardant composition in divided form (granules, powder), optionally coated with dispersing and protective agents, such as microwaxes, fatty acids.
  • the dehydrating agent can be used predispersed in a polymer material (for example a semicrystalline ethylene/propylene rubber).
  • the flame-retardant compositions thus obtained can be used to coat the conductor directly, or to make an outer sheath on the conductor which has been precoated with an insulating layer.
  • the extrusion can take place in two separate phases, the inner layer being extruded on the conductor in a first passage and the outer layer being extruded on the inner layer in a second passage.
  • the coating process can take place in a single passage, for example by means of the "tandem" technique, in which two separate extruders arranged in series are used, or alternatively by coextrusion with a single extrusion head.
  • the temperature at which the flame-retardant composition is extruded can vary within a wide range and is predetermined as a function of the extrusion rate to be obtained.
  • the extrusion rate in fact depends on the viscosity of the composition in the molten state and thus on its temperature. In turn, the viscosity depends mainly on the type of polymer base and on the type and amount of flame-retardant filler used.
  • the minimum extrusion temperature for the composition is generally not less than the plasticization temperature of the polymer base, while the maximum extrusion temperature is predetermined so as to avoid degradation or decomposition of the polymer base and/or of the flame-retardant filler.
  • the temperature at which the flame-retardant composition is extruded is generally between 160°C and 320°C, preferably between 200°C and 280°C.
  • the present description is mainly directed towards the production of self-extinguishing cables by extrusion
  • the advantages deriving from the use of the dehydrating agent according to the present invention can be evident in different extrusion or moulding processes for the general production of rubber articles in which hygroscopic fillers are used, for example junction boxes for electrical cable junctions or terminals, in particular when high processing temperatures are required in order to obtain increased fluidity of the material to be extruded or moulded.
  • low-voltage generally means a voltage of less than 2 kV, preferably less than 1 kV.
  • the cable in Fig. 1 comprises a conductor (1), an inner layer (2) which functions as an electrical insulator, and an outer layer (3) which functions as a protective sheath with flame-retardant properties.
  • the inner layer (2) can consist of a crosslinked or non-crosslinked, halogen-free polymer composition with electrical insulation properties, which is known in the art, chosen, for example, from: polyolefins (homopolymers or copolymers of various olefins), and mixtures thereof.
  • polyethylene in particular linear low-density PE (LLDPE); polypropylene (PP); propylene/ethylene thermoplastic copolymers; ethylene/propylene rubbers (EPR) or ethylene/propylene/diene rubbers (EPDM); natural rubbers; butyl rubbers; ethylene/vinyl acetate (EVA) copolymers; ethylene/methyl acrylate (EMA) copolymers; ethylene/ethyl acrylate (EEA) copolymers; ethylene/butyl acrylate (EBA) copolymers; ethylene/ ⁇ -olefin copolymers.
  • PE polyethylene
  • LLDPE linear low-density PE
  • PP polypropylene
  • EPR ethylene/propylene rubbers
  • EPDM ethylene/propylene/diene rubbers
  • EVA ethylene/vinyl acetate copolymers
  • EMA ethylene/methyl acrylate
  • EAA ethylene/ethyl acrylate
  • a self-extinguishing cable which can be made according to the present invention can consist of a conductor coated directly with the flame-retardant composition, without interposition of other insulating layers.
  • the flame-retardant coating also functions as an electrical insulator.
  • a thin polymer layer which functions as an anti-abrasive agent, optionally combined with a suitable pigment in order to give a coloration for identification purposes, can then be added externally.
  • the flame-retardant compositions were prepared in a closed Banbury mixer (mixing chamber volume: 1200 cm 3 ) filled to a volumetric level of 95 %.
  • the mixing was carried out in two phases. In the first phase, the components of the compound, with the exception of the dehydrating agent, were mixed together until a temperature of about 200°C was reached, so as to ensure good dispersion of the components and to reduce the amount of moisture present in the filler.
  • the dehydrating agent was then added, while keeping the mixing temperature at about 200°C.
  • Self-extinguishing cables were produced by extruding the compositions prepared as described above on a wire of red copper (cross-section 2.5 mm 2 ) in an extruder with a cylinder 120 mm in diameter and with a on a wire of red copper (cross-section 2.5 mm 2 ) in an extruder with a cylinder 120 mm in diameter and with a length equal to 25 diameters (final thickness of the flame-retardant layer: 0.8 mm).
  • the temperature of the composition in the extruder was kept at about 250°C, with an extrusion rate of 900 m/min.
  • the flame-retardant coatings thus obtained were subjected to mechanical tensile strength tests according to CEI standard 20-34 ⁇ 5.1. The results are given in Table 1, as the average value obtained over five samples taken at random from each cable produced. All of the cables produced passed the flame-resistance test according to IEC standard 332-1, which consists in subjecting a 60 cm long sample, placed vertically, to the direct action of a Bunsen-burner flame applied for 1 min at an angle of 45° relative to the sample.

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Insulated Conductors (AREA)
  • Fireproofing Substances (AREA)
  • Organic Insulating Materials (AREA)
EP99965500A 1998-12-24 1999-12-20 Process for producing self-extinguishing cables with low-level production of fumes and flame-retardant compositions used therein Expired - Lifetime EP1149390B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP99965500A EP1149390B1 (en) 1998-12-24 1999-12-20 Process for producing self-extinguishing cables with low-level production of fumes and flame-retardant compositions used therein

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
EP98124648 1998-12-24
EP98124648 1998-12-24
US11559399P 1999-12-01 1999-12-01
US115593P 1999-12-01
EP99965500A EP1149390B1 (en) 1998-12-24 1999-12-20 Process for producing self-extinguishing cables with low-level production of fumes and flame-retardant compositions used therein
PCT/EP1999/010131 WO2000039810A1 (en) 1998-12-24 1999-12-20 Process for producing self-extinguishing cables with low-level production of fumes, and flame-retardant compositions used therein

Publications (2)

Publication Number Publication Date
EP1149390A1 EP1149390A1 (en) 2001-10-31
EP1149390B1 true EP1149390B1 (en) 2011-04-06

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EP (1) EP1149390B1 (ko)
KR (1) KR100622617B1 (ko)
AU (1) AU754014B2 (ko)
CA (1) CA2356870C (ko)
HU (1) HU227773B1 (ko)
ID (1) ID30038A (ko)
NZ (1) NZ512541A (ko)
WO (1) WO2000039810A1 (ko)

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US8765035B2 (en) 2003-12-24 2014-07-01 Prysmian Cavi E Sistemi Energia S.R.L. Process for manufacturing a self-extinguishable cable
EP1789974A1 (en) 2004-06-28 2007-05-30 Prysmian Cavi e Sistemi Energia S.r.l. Cable with environmental stress cracking resistance
KR100803441B1 (ko) 2006-02-22 2008-02-13 엘에스전선 주식회사 저발연 고신율 절연재 제조용 조성물
FR2913908B1 (fr) * 2007-03-19 2009-06-05 Nexans Sa Procede de fabrication d'une couche reticulee pour cable d'energie et/ou de telecomunication
US8901426B2 (en) 2008-08-05 2014-12-02 Prysmian S.P.A. Flame-retardant electrical cable
KR101132922B1 (ko) 2009-12-11 2012-04-06 호남석유화학 주식회사 산화칼슘을 이용하여 취기 및 총휘발성 유기화합물을 저감한 폴리올레핀 조성물.
ITMI20111572A1 (it) 2011-09-01 2013-03-02 R & D Innovaction S R L Composizioni antifiamma e relativo processo di produzione
RU2625323C1 (ru) * 2016-03-18 2017-07-13 Общество с ограниченной ответственностью фирма "Проминвест Пластик" Электроизоляционная композиция
KR102398314B1 (ko) * 2020-11-18 2022-05-16 강소영 전기화재 징후 감시용 절연재 및 그 제조방법

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JPS59500816A (ja) * 1982-05-07 1984-05-10 エ−／エス．ノルスク．カ−ベルフアブリ−ク 防火材料
JPH08165468A (ja) * 1994-12-12 1996-06-25 Erika Balle 防火物質及び防火物質の製造方法及び防火物質を付着する方法

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NZ512541A (en) 2003-07-25
HUP0104862A3 (en) 2002-07-29
AU754014B2 (en) 2002-10-31
ID30038A (id) 2001-11-01
AU2099400A (en) 2000-07-31
KR100622617B1 (ko) 2006-09-11
KR20010086464A (ko) 2001-09-12
HU227773B1 (hu) 2012-02-28
EP1149390A1 (en) 2001-10-31
CA2356870C (en) 2009-09-08
CA2356870A1 (en) 2000-07-06
WO2000039810A1 (en) 2000-07-06
HUP0104862A2 (hu) 2002-04-29

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